CN106700077A - Preparation method of high-temperature-resistant anti-cracking MDQ silicon resin - Google Patents
Preparation method of high-temperature-resistant anti-cracking MDQ silicon resin Download PDFInfo
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- CN106700077A CN106700077A CN201611038869.0A CN201611038869A CN106700077A CN 106700077 A CN106700077 A CN 106700077A CN 201611038869 A CN201611038869 A CN 201611038869A CN 106700077 A CN106700077 A CN 106700077A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
Abstract
The invention relates to a preparation method of high-temperature-resistant anti-cracking MDQ silicon resin. The method comprises the following steps of adding acid, divinyl tetramethyl disiloxane, hexamethyldisiloxane and dimethyl dialkoxy silane, alcohol and 2 to 5g of water into a four-opening bottle; performing stirring; heating the materials to 25 DEG C; performing reaction for 1 to 2 hours; after the reaction is completed, dripping the rest total amount of water and silicate ester at the same time at the room temperature; controlling the temperature in a system to be between 30 and 40 DEG C; after the dripping completion, performing reaction for 1 to 2 hours at 70 DEG C; then, distilling out alcohol in the system; then, adding methylbenzene and alkali with the same mass as the theoretical synthesis resin to regulate the system pH to be 9 to 10; performing reaction for 1 hour at 90 DEG C; then, raising the temperature to distill out the rest alcohol and water; finally, lowering the temperature; performing neutralization by acid; performing water washing until the system pH is 6 to 7; performing rotary evaporateion at 120 DEG C to remove methylbenzene so as to obtain the silicon resin. The DMQ silicon resin prepared by the method provided by the invention is mainly used for reinforcing agents of encapsulation glue, organic silicon additives and organic silicon mold plastics.
Description
Technical field
The present invention relates to preparation method of the high temperature resistant without cracking methyl ethylene MDQ silicones, belong to the synthesis of silicones
Technical field.
Background technology
Silicones is used as the class product earlier that come out in organosilicon material, because it has dielectric constant excellent, performance
Stably, the characteristic such as excellent resistance to oxidation, chemicals-resistant, electrical insulating property, radiation hardness and weatherability.Therefore silicones can be used for electric exhausted
Edge paint, coating, moulding compound, laminate layer material, ingot stripper etc., have wide at aspects such as Aero-Space, electronic device, building, machineries
General purposes.
In existing technology, the report about MDQ silicones is little, only the synthesis side of methyl vinyl MQ silicon resin
Method.It is big to there is rigidity in MQ resins, is easily caused film high temperature cracking in formula, reinforcing effect substantially, viscosity even solid greatly,
There is difficulty of processing in later stage formula process big, the problems such as high cost.MDQ silicones is keeping original MQ resins reinforcement
On the premise of effect, flexible link (D links) is introduced, the high temperature cracking for substantially improving or even solving original film is asked
Topic, reduces the viscosity of resin, is easy to post-production.
The content of the invention
For the deficiency of existing MQ silicones, a kind of high temperature problem of Cracking that can substantially improve film of present invention offer,
Reduce the MDQ silicones synthetic methods of the viscosity of resin.
Technical scheme is as follows：A kind of preparation method of high temperature resistant without cracking MDQ silicones, including：At four mouthfuls
Acid, vinyl double seal head, HMDO, dimethyldialkylammonium TMOS, alcohol and 2-5g water are added in bottle, stirred, added
Hot to 25 DEG C are reacted 1-2 hours, remaining total water and esters of silicon acis are added dropwise simultaneously at room temperature after the completion of reaction, in control system
Temperature between 30-40 DEG C, after completion of dropping at 70 DEG C react 1-2 hours, then steam the alcohol in system, be subsequently adding with
The toluene of the quality such as theoretical synthetic resin and the pH=9-10 of alkali regulation system, 90 DEG C are reacted 1 hour, are then heated up and are steamed system
Interior remaining alcohol and water, finally lowers the temperature, is neutralized with acid, is washed to the pH=6-7 of system again；120 DEG C of backspins are evaporated off toluene i.e.
Obtain silicones；
The acid, vinyl double seal head, HMDO, dimethyldialkylammonium TMOS, alcohol, water and esters of silicon acis
Mass ratio is (1.18-1.99)：(5.58-38.50)：(30.46-113.24)：(60.11-240.44)：(11.80-19.95)：
(50.20-120.80)：208.33.
According to currently preferred, the dimethyldialkylammonium TMOS is dimethyldimethoxysil,ne, dimethyl two
One kind in Ethoxysilane；
According to currently preferred, the compatibility of increase system played using alcohol is added and suppresses to react too fast；
According to currently preferred, the esters of silicon acis is in methyl silicate, tetraethyl orthosilicate, positive isopropyl silicate
Kind；
According to currently preferred, the acid is hydrochloric acid, sulfuric acid, phosphoric acid, Emathlite, trifluoromethane sulfonic acid and acidity sun
One kind in ion exchange resin；
According to currently preferred, the consumption of water is esters of silicon acis and the 2.4- of dimethyldialkylammonium TMOS total moles quality
3.6 times；
According to currently preferred, the alcohol is ethanol, methyl alcohol, isopropanol；
According to currently preferred, the alkali is Na2CO3、NaHCO3、K2CO3、KHCO3, one kind in NaOH, KOH；
According to currently preferred, the reaction temperature is 30~120 DEG C；
According to currently preferred, speed of agitator is 200-450 revs/min；
According to currently preferred, vinyl mass percent is 1.5%-6%；
According to currently preferred, the value of R/Si is 1.1-1.8；
According to currently preferred, the methyl ethylene MDQ silicones of synthesis can accurately be controlled by deviating from the amount of alcohol
The surplus of alkoxy processed；
According to currently preferred, the reactor is equipped with thermometer, constant pressure funnel, spherical condensation tube, tetrafluoro
The four round flask of stirring rod.
MDQ silicones prepared by the present invention is mainly used in the reinforcing agent of packaging plastic, organosilicon adhesive and organosilicon molding
Material.
Specific embodiment
Peering principle of the invention and feature are described below, and example is served only for explaining the present invention, is not intended to
Limit the scope of the present invention.
Embodiment 1
Concentrated hydrochloric acid, 15.13g vinyl double seal heads, the 67.70g HMDOs of 1.77g are added in four-hole bottle
MM, 60.11g dimethyldiethoxysilane, the ethanol of 15.10g and 3.00g water are 300 turns/min, react at 25 DEG C in rotating speed
1 hour, the water of 57.40g and the tetraethyl orthosilicate of 208.33g is added dropwise after the completion of reaction simultaneously at room temperature, in control system
Temperature is reacted 2 hours after completion of dropping between 30 DEG C at 70 DEG C, and then 80 DEG C of ethanol steamed in system, is subsequently adding
The pH=9 of 172.10g toluene and appropriate NaOH regulation systems, reacts 1 hour at 90 DEG C, then heats to 120 DEG C and steams system
Interior remaining second alcohol and water, finally lower the temperature again, in acid adding and, be washed to the pH=6-7 of system；120 DEG C of backspins steam system
Interior toluene is to obtain methyl ethylene MDQ silicones, and its yield is 93%.
Embodiment 2
Concentrated hydrochloric acid, 15.13g vinyl double seal heads, the 67.70g HMDOs of 1.17g are added in four-hole bottle
MM, 60.11g dimethyldimethoxysil,ne, the methyl alcohol of 15.10g and 3.00g water are 300 turns/min, react at 25 DEG C in rotating speed
1 hour, the water of 56.00g and the methyl silicate of 152.22g is added dropwise after the completion of reaction simultaneously at room temperature, in control system
Temperature is reacted 2 hours after completion of dropping at 35 DEG C at 70 DEG C, and then 70 DEG C of methyl alcohol steamed in system, is subsequently adding 163.61g
The pH=9 of toluene and appropriate KOH regulation systems, at 90 DEG C react 1 hour, then heat to 120 DEG C steam it is remaining in system
First alcohol and water, finally lower the temperature again, in acid adding and, be washed to the pH=6-7 of system；120 DEG C of backspins steam the toluene in system
Methyl ethylene MDQ silicones is obtained, its yield is 94%.
Embodiment 3
Concentrated hydrochloric acid, 15.13g vinyl double seal heads, the 67.70g HMDOs of 1.50g are added in four-hole bottle
MM, 60.11g dimethyldimethoxysil,ne, the isopropanol of 15.10g and 3.00g water rotating speed be 300 turns/min, at 25 DEG C it is anti-
Answer 1 hour, the water of 69.00g and the positive isopropyl silicate of 152.22g, control system is added dropwise after the completion of reaction simultaneously at room temperature
Interior temperature is reacted 2 hours after completion of dropping at 40 DEG C at 70 DEG C, and then 90 DEG C of isopropanols steamed in system, are subsequently adding
163.61g toluene and appropriate Na2CO3The pH=9 of regulation system, reacts 1 hour at 90 DEG C, then heats to 120 DEG C and steams system
Interior remaining isopropyl alcohol and water, finally lower the temperature again, in acid adding and, be washed to the pH=6-7 of system；120 DEG C of backspins steam body
Toluene in system is to obtain methyl ethylene MDQ silicones, and its yield is 90%.
Embodiment 4
The concentrated sulfuric acid, 17.00g vinyl double seal heads, the 46.08g HMDOs of 1.60g are added in four-hole bottle
MM, 60.11g dimethyldiethoxysilane, the ethanol of 19.10g and 3.00g water are 300 turns/min, react at 25 DEG C in rotating speed
1 hour, the water of 57.40g and the tetraethyl orthosilicate of 208.33g is added dropwise after the completion of reaction simultaneously at room temperature, in control system
Temperature is reacted 2 hours after completion of dropping at 40 DEG C at 70 DEG C, and then 80 DEG C of ethanol alcohol steamed in system, is subsequently adding
163.10g toluene and appropriate NaHCO3The pH=9 of regulation system, reacts 1 hour at 90 DEG C, then heats to 120 DEG C and steams body
Remaining second alcohol and water in system, finally lower the temperature again, in acid adding and, be washed to the pH=6-7 of system.120 DEG C of backspins steam body
Toluene in system is to obtain methyl ethylene MDQ silicones, and its yield is 93%.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all it is of the invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (6)
1. a kind of high temperature resistant without cracking MDQ silicones preparation method, it is characterised in that including：Acid, second are added in four-hole bottle
Alkenyl double-seal head, HMDO, dimethyldialkylammonium TMOS, alcohol and 2-5g water, stir, are heated to 25 DEG C of reaction 1-
2 hours, remaining total water and esters of silicon acis is added dropwise simultaneously at room temperature after the completion of reaction, the temperature in control system is in 30-40
Between DEG C, reacted 1-2 hours at 70 DEG C after completion of dropping, then steam the alcohol in system, be subsequently adding and theoretical synthetic resin
Etc. the toluene and the pH=9-10 of alkali regulation system of quality, 90 DEG C are reacted 1 hour, then heat up steam in system remaining alcohol and
Water, finally lowers the temperature, is neutralized with acid, is washed to the pH=6-7 of system again；120 DEG C of backspins are evaporated off toluene and obtain final product silicones；
The quality of the acid, vinyl double seal head, HMDO, dimethyldialkylammonium TMOS, alcohol, water and esters of silicon acis
Than being (1.18-1.99)：(5.58-38.50)：(30.46-113.24)：(60.11-240.44)：(11.80-19.95)：
(50.20-120.80)：208.33.
2. preparation method according to claim 1, it is characterised in that the dimethyldialkylammonium TMOS is dimethyl two
One kind in methoxy silane, dimethyldiethoxysilane.
3. preparation method according to claim 1, it is characterised in that the esters of silicon acis is methyl silicate, positive silicic acid second
One kind in ester, positive isopropyl silicate.
4. preparation method according to claim 1, it is characterised in that the acid be hydrochloric acid, sulfuric acid, phosphoric acid, Emathlite,
One kind in trifluoromethane sulfonic acid and acid cation exchange resin.
5. preparation method according to claim 1, it is characterised in that the alcohol is in ethanol, methyl alcohol, isopropanol
Kind；The alkali is Na2CO3、NaHCO3、K2CO3、KHCO3, one kind in NaOH, KOH.
6. preparation method according to claim 1, it is characterised in that speed of agitator is 200-450 revs/min.
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| CN201611038869.0A CN106700077A (en) | 2016-11-11 | 2016-11-11 | Preparation method of high-temperature-resistant anti-cracking MDQ silicon resin |
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| CN201611038869.0A CN106700077A (en) | 2016-11-11 | 2016-11-11 | Preparation method of high-temperature-resistant anti-cracking MDQ silicon resin |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109722218A (en) * | 2018-12-25 | 2019-05-07 | 烟台德邦科技有限公司 | A kind of electrolyte resistance sealant and preparation method thereof |
| CN110698674A (en) * | 2019-02-18 | 2020-01-17 | 杭州师范大学 | Fluorine-containing MDQ type silicon resin capable of being chemically crosslinked and cured and preparation method thereof |
| CN111410932A (en) * | 2020-05-14 | 2020-07-14 | 南京科矽新材料科技有限公司 | High-flexibility and high-adhesion methyl organosilicon adhesive for L ED |
| CN111410744A (en) * | 2019-01-04 | 2020-07-14 | 中昊晨光化工研究院有限公司 | MDQ silicon resin containing phenyl and preparation method thereof |
| CN112522965A (en) * | 2020-11-27 | 2021-03-19 | 广东鼎立森新材料有限公司 | Organic silicon synthetic leather and preparation method thereof |
| CN112745505A (en) * | 2020-12-28 | 2021-05-04 | 广东标美硅氟新材料有限公司 | Alkyl modified MDQ type silicon resin and preparation method and application thereof |
| CN115216154A (en) * | 2021-05-28 | 2022-10-21 | 江苏睿玮新材料科技有限公司 | Thermally stable two-component heat-conducting gel and preparation method thereof |
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| CN102898648A (en) * | 2012-05-11 | 2013-01-30 | 杭州师范大学 | Chemical crosslinking-curable phenyl MDQ-type silicone resin and preparation method thereof |
| CN104892938A (en) * | 2015-06-26 | 2015-09-09 | 深圳市森日有机硅材料有限公司 | MDQ phenyl hydrogen-containing silicon resin and preparing method thereof |
| CN106084230A (en) * | 2016-07-15 | 2016-11-09 | 烟台德邦先进硅材料有限公司 | A kind of preparation method of low thermal weight loss low-refraction Narrow Molecular Weight Distribution silicones |
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| CN102898648A (en) * | 2012-05-11 | 2013-01-30 | 杭州师范大学 | Chemical crosslinking-curable phenyl MDQ-type silicone resin and preparation method thereof |
| CN104892938A (en) * | 2015-06-26 | 2015-09-09 | 深圳市森日有机硅材料有限公司 | MDQ phenyl hydrogen-containing silicon resin and preparing method thereof |
| CN106084230A (en) * | 2016-07-15 | 2016-11-09 | 烟台德邦先进硅材料有限公司 | A kind of preparation method of low thermal weight loss low-refraction Narrow Molecular Weight Distribution silicones |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109722218A (en) * | 2018-12-25 | 2019-05-07 | 烟台德邦科技有限公司 | A kind of electrolyte resistance sealant and preparation method thereof |
| CN109722218B (en) * | 2018-12-25 | 2021-05-04 | 烟台德邦科技股份有限公司 | Electrolyte-resistant sealant and preparation method thereof |
| CN111410744A (en) * | 2019-01-04 | 2020-07-14 | 中昊晨光化工研究院有限公司 | MDQ silicon resin containing phenyl and preparation method thereof |
| CN111410744B (en) * | 2019-01-04 | 2021-06-22 | 中昊晨光化工研究院有限公司 | MDQ silicon resin containing phenyl and preparation method thereof |
| CN110698674A (en) * | 2019-02-18 | 2020-01-17 | 杭州师范大学 | Fluorine-containing MDQ type silicon resin capable of being chemically crosslinked and cured and preparation method thereof |
| CN111410932A (en) * | 2020-05-14 | 2020-07-14 | 南京科矽新材料科技有限公司 | High-flexibility and high-adhesion methyl organosilicon adhesive for L ED |
| CN111410932B (en) * | 2020-05-14 | 2022-02-22 | 南京科矽新材料科技有限公司 | Methyl organosilicon adhesive with excellent flexibility and strong adhesion for LED |
| CN112522965A (en) * | 2020-11-27 | 2021-03-19 | 广东鼎立森新材料有限公司 | Organic silicon synthetic leather and preparation method thereof |
| CN112522965B (en) * | 2020-11-27 | 2022-03-01 | 广东鼎立森新材料有限公司 | Organic silicon synthetic leather and preparation method thereof |
| CN112745505A (en) * | 2020-12-28 | 2021-05-04 | 广东标美硅氟新材料有限公司 | Alkyl modified MDQ type silicon resin and preparation method and application thereof |
| CN112745505B (en) * | 2020-12-28 | 2022-05-03 | 广东标美硅氟新材料有限公司 | Alkyl modified MDQ type silicon resin and preparation method and application thereof |
| CN115216154A (en) * | 2021-05-28 | 2022-10-21 | 江苏睿玮新材料科技有限公司 | Thermally stable two-component heat-conducting gel and preparation method thereof |
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Effective date of registration: 20190220 Address after: 264006 Renewable Resource Processing Demonstration Zone No. 3-10 Kaifeng Road, Yantai Development Zone, Shandong Province Applicant after: Yantai Darbond Technology Co., Ltd. Address before: 264000 Yantai Development Zone, Shandong Province, 3-3 Kaifeng Road Resource Regeneration and Processing Demonstration Zone Applicant before: Yantai Debang Advanced Silicon Materials Co.,Ltd. |
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Application publication date: 20170524 |
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